Processes to make olive drab to greenish-gold mineral dye shades for cellulosics

ABSTRACT

Olive drab to greenish-gold mineral dye shades are imparted to cellulosic textiles by a two-solution aqueous process wherein critical proportions of ferrous salts and chromic chloride are mixed in a first aqueous solution, applied to the textile and dried, then a mixture of sodium hydroxide and sodium carbonate are applied in a second aqueous solution, and the color developed upon the drying-curing step. The coloration is controllably olive drab when the ferrous salt content is low and controllably greenish-gold when the ferrous salt content is high.

United States Patent 11 1 Conner Oct. 28, 1975 PROCESSES TO MAKE OLIVE DRAB TO GREENISH-GOLD MINERAL DYE SHADES FOR CELLULOSICS [75] Inventor: .Charles J. Conner, Matairie, La.

[73] Assignee: The United States of America as represented by the Secretary of Agriculture, Washington, DC.

[22] Filed: June 28, 1973 [21] Appl. No.: 374,585

[52] US. Cl. 8/52; 8/542; 252/8.6 [51] Int. Cl. C09B 61/100; DO6P 1/00;

DO6P 3/60; DO6M 00/00 [58] Field of Search 8/52; 252/8.6

[56] References Cited UNITED STATES PATENTS 10/1928 white"; 8/52 8/1937 White 8/52 2/l960 Crosland 8/52 2/1974 Conner i. 8/52 Primary ExaminerBenjamin R. Padgett Assistant Examiner-Donald P. Walsh Attorney, Agent, or F irm--M. Howard Silverstein; Max D. Hensley [5 7] ABSTRACT Olive drab to greenish-gold mineral dye shades are im- 4 Claims, N0 Drawings 1 PROCESSES TO MAKE OLIVE DRAB TO GREENISH-GOLD MINERAL DYE SHADES FOR CELLULOSICS I The prior art shows that mineral colors are produced by treating cellulosics with metal salts in aqueous solution, followed by treatment withan alkali to produce the metal hydroxide or hydrated oxide in the cellulosic (as pigment), resulting in colored-mineral dyeings.

These colors are simple double decomposition" reaction products, andare well known in the trade. However, when a ferrous salt is incorporated into a chromic chloride solution, the ferrous salt is capable of producing basic ferroso-ferric hydrated oxides through partial oxidation and heating with excess concentrated alkalis. Since our processing can be demonstrated to be a series of reactions, over and above simple double decomposition, it is unique and novel in the field of mineral dyeings, offering several new and attractive color shades for stable textile-mineral dyeing.

The present invention consists of treating an aqueous solution of chromic chloride with ferrous salt. (sulphate), to produce an aqueous bath of chromic chloride and ferrous 120-130C, the intimate chromic chloride andferro us sulphate salts are deposited and 'dried in the cellulosic, producing a .pure dark green" 150-155C for 2 to 3 minutes. At the end of this time, the color changes from pure green" to a golden" or yellow-brown shade. Heating in contact with the excess alkali produces this change at about 150C. The dyed cellulosic is then hot water washed to remove soluble matter, and dried at 130150C for 2 to 3 minutes. The mineral dyeingis uniform and colored in the 'olive drab to greenish-gold" range, dependingion the ratio of ferrous salt to'chromiumin the first bath.

The main objectof the inventionis to provide a unique'process'fordyeing olive drab to greenish-gold mineral dye shades on cellulosics, using low costchemicals and conventional mill equipment, to produce highly desirable attractive mineral dye color shades.

A second object of the invention is to use conventional chromic chloride, familiar to most textile finishers, inexpensive and readily available ferrous sulphate, and alkali chemicals which are inexpensive and coriventionally used in textile mills, for the'development of dye shades of very attractive appearance from inexpensive materials, capable of being finished with hydrophobic wax water repellents, as with other conventional mineral dyeings.

Utility of the invention is obviously in the field of mineral dyeings and weatherable goods, such as pigmented (dyed) cellulosics for tents, sails, tarpaulins, umbrellas, awnings, ropes, shoe linings, boat covers, canvas shoes,'upholstery, etc.

SUMMARY This invention can best be described as one disclosing specific inorganic chemical formulations and a process for imparting to cellulosic textiles durable greenish-yellow (golden) to olive drabcoloration through mineral dyeing, theprocess comprising impregnating a cellulosic textile with an aqueous solution containing ferrous sulphate and liquid 89% Cr chromic chloride solution, wherein the ferrous sulphate is about 1.5% to 2.95% of the solution and the chromic chloride content is about from 78% to 79%; drying the wet impregnated textile at about from to C for about 2 to 3 minutes; impregnating the textile again, with an aqueous alkali solution containing about 5% to 15% of sodium hydroxide and about from 5% to 25% sodium carbonate; drying-curing the wet impregnated textile at about from to C for about 2 to 3 minutes to develop the color; and hot water-washing at a temperature of about 55C for about from 2 to 3 minutes to re- EXAMPLE 1 (Bath) Olive Drab Mineral Dyeing Procedure For i Scoured Cotton Duck 1 l BATH A 40.0 grams Chromic Chloride Solution (8%9% Chromium Metal Content)* 10.0 grams Water (distilled or soft) 0.8 gram Ferrous sulphate (heptahydrate) crystals 50.8 grams Bath A (For Olive Drab Dye Shade) BATH B 5.0 grams Sodium Hydroxide Pellets (Caustic Soda) 15.0 grams Soda Ash (Sodium Carbonate) Anhydrous 80.0 grams Water (distilled or soft) 100.0 grams Bath B (Alkali) Industrial chromic chloride is supplied as a liquid with 8% to 9% chromium metal content. 40 grains of. this liquid in a 50.8 gram Bath (A) 78.7% of Bath (A).

EXAMPLE 2 Procedure for ,Olive Drab Mineral Dyeing Procedure on CottonScoured Duck A 2X4 inch section of scoured cotton 9'02. duck was wetted thoroughly in Bath A', the excess squeezed out through rollers, and the wet fabric heated in the oven at 120-130C for 2to 3 minutes, until the dry treated fabric was pure-dark green." The'dry fabric was then immersed and thoroughly wetted with Bath B,

EXAMPLE 3 Demonstration To Show That The Alkali Must Be Present in Curing After Double Decomposition Baths A and B were prepared as in Example 1. The scoured duck fabric was wetted, squeezed, and oven dried at 120-l 30C with Bath A. The fabric was then wetted thoroughly in Bath B, squeezed, and washed free of alkali and salts with hot tap waterfThe fabric was dyed a grayish-green. It was then oven dried for 2 to 3 minutes at l30150C. A grayish-green mineral dyeing resulted, without the yellowish-green color of '5 Olive Drab, showing that cure without contact with free alkali did not produce the necessary conversion to "Olive Drab.

EXAMPLE 4 (Bath) Greenish-Gold Mineral Dyeing Procedure For Scoured Duck BATH A 40.0 grams Chromic Chloride Solution (8%-9% chromium metal content)* 10.0 grams Water (Distilled or soft) 1.0 gram Ferrous Sulphate (heptahydrate crystals) 51.0 grams Bath A (Greenish-Gold) BATH B 5.0 grams Sodium Hydroxide Pellets (Caustic Soda) 15.0 grams Soda Ash (Sodium Carbonate) Anhydrous 80.0 grams Water (Distilled or soft) 100.0 grams Bath B (Greenish-Gold) Alkali (Note: Both baths should be uniform, clear, solutions) Industrial chromic chloride is supplied as a liquid with 8% to 9% chromium metal content. 40 grams of this liquid in a 51.0 gram Bath (A) 78% of Bath (A).

EXAMPLE Procedure for Greenish-Gold Mineral Dyeing on Scoured Duck A 3X4 inch piece of scoured 9 oz. duck was treated with Bath A according to procedure in Example 2, followed by treatment with Bath B according to procedure in Example 2. Oven heating and washing and drying procedures were the same as in Example 2. A uniform greenish-gold mineral dyeing resulted.

EXAMPLE 6 0.25 gm. Ferrous SulphateGreen mineral dyeing 0.50 gm. Ferrous SulphateBright mediumgreen 0.80 gm. Ferrous Sulphate0live Drab shade 1.00 gm. Ferrous Sulphate-Greenish-Gold dye shade 1.50 gm. Ferrous Sulphate-Brown(greenish) dye shade v in Bath A, (of Example 6), all other components (other than Ferrous Sulphate remain constant, per Example 1. Applications were made with 9 oz. scoured cotton army duck in each evaluation.

'1" With 5 gms. NaOH and 5 gms. Na CO the water content is q g' f With 15 gms. NaOH and 25 gms. C Bath (B) Na cQa, the water content is 60% EXAMPLE 7 EXAMPLE 8 Dyed swatches of both olive drab and greenish gold were exposed v to outdoor weathering on wooden frames. After one month, no evidence of color change was noted, and the mineral dyeings were stable to sunlight and weathering.

I claim:

1. A process for imparting to cellulosic textiles durable greenish-yellow (golden) to olive drab coloration through mineral dyeing, the process comprising impregnating a cellulosic textile with an aqueous solution containing ferrous sulphate and liquid 89% Cr chromic chloride solution, wherein the ferrous sulphate is about 1.5% to 2.95% of the solution and the chromic chloride solution content is about from 78% to 79%;

drying the wet impregnated textile at about from to C for about 2to 3 minutes; impregnating the textile again, with an aqueous alkali solution containing about 5% to 15% of sodium hydroxide and about from 5% to 25% sodium carbonate; drying-curing the wet impregnated textile at about from to C for about 2 to 3 minutes to develop the color; and hot water-washing at a temperature of about 55C for about from 2 to 3 minutes to remove residual alkalies; and drying at temperatures about from 130 to 150C for about 2 to 3 minutes.

2. The process of claim 1 wherein the ferrous sulphate in the first solution is about 1.50% to yield a cellulosic textile with an olive drab coloration.

3. The process of claim 1 wherein the ferrous sulphate in the first solution is about 1.96% to yield a cellulosic textile with a greenish-gold coloration.

4. The process of claim 1 wherein the ferrous sulphate in the first solution is about 2.95% to yield a brownish shade of greenish-gold. 

1. A PROCESS FOR IMPARTING TO CELLOUSIC TEXTILES DURABLE GREENISH-YELLOW (GOLDEN) TO OLIVE DRAB COLORATION THROUGH MINERAL DYEING, THE PROCESSED COMPRISING IMPREGNATING A CELLULOSIC TEXTILE WITH AN AQUEOUS SOLUTION CONTAINING FERROUS SULPHATE AND LIQUID 8-9% CR CHROMIC CHLORIDE SOLUTION, WHEREIN THE FERROUS SULPHATE IS ABOUT 1.5% TO 2.95% OF THE SOLUTION AND THE CHROMIC CHLORIDE SOLUTION CONTENT IS ABOUT FROM 78% TO 79%, DRYING THE WET IMPREGNATED TEXTILE AT ABOUT FROM 120* TO 130*C FOR ABOUT 2 TO 3 MINUTES, IMPREGNATING THE TEXTILE AGAIN, WITH AN AQUEOUS ALKALI SOLUTION CONTAINING ABOUT 5% TO 15% OF SODIUM HYDROXIDE AND ABOUT FROM 5% TO 25% SODIUM CARBONATE, DRYING-CURING THE WET IMPREGNATED TEXTILE AT ABOUT FROM 150* TO 155*C FOR ABOUT 2 TO 3 MINUTES TO DEVELOP THE COLOR, AND HOT WATER-WASHING AT A TEMPERATURE OF ABOUT 55*C FOR ABOUT FROM 2 TO 3 MINUTES TO REMOVE RESIDUAL ALKALIES, AND DRYING AT TEMPERATURES ABOUT FROM 130* TO 150*C FOR ABOUT 2 TO 3 MINUTES.
 2. The process of claim 1 wherein the ferrous sulphate in the first solution is about 1.50% to yield a cellulosic textile with an olive drab coloration.
 3. The process of claim 1 wherein the ferrous sulphate in the first solution is about 1.96% to yield a cellulosic textile with a greenish-gold coloration.
 4. The process of claim 1 wherein the ferrous sulphate in the first solution is about 2.95% to yield a brownish shade of greenish-gold. 